CN107337178B - Process for recycling PSA desorption gas and catalytic regeneration flue gas of oil refinery - Google Patents
Process for recycling PSA desorption gas and catalytic regeneration flue gas of oil refinery Download PDFInfo
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- CN107337178B CN107337178B CN201710413757.7A CN201710413757A CN107337178B CN 107337178 B CN107337178 B CN 107337178B CN 201710413757 A CN201710413757 A CN 201710413757A CN 107337178 B CN107337178 B CN 107337178B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of petrochemical industry, and discloses a PSA (pressure swing adsorption) solution for an oil refineryA process for recycling suction gas and catalytic regeneration flue gas. The process flow comprises the following steps: PSA desorption gas is reacted by a hydrocarbon steam hydrogen production conversion furnace under the action of a catalyst to generate conversion gas; the catalytic regeneration flue gas is compressed and heated, then mixed with the converted gas, enters a medium-temperature shift reactor, and reacts under the action of a catalyst to obtain shifted gas; the conversion gas is subjected to heat exchange and temperature reduction and then sequentially enters a conversion gas-water separation tank and a low-temperature methanol washing unit to recover CO2The methanation unit removes the total carbon and then sends the total carbon to the ammonia synthesis unit, NH is obtained by the circular reaction under the catalysis3And (5) producing the product. The invention realizes the high-efficiency utilization of hydrogen, hydrocarbon materials and CO in the desorption gas, and concentrates and catalyzes the regenerated flue gas and the CO in the desorption gas2The purity is more than 99 percent, and the method has remarkable energy-saving and emission-reducing effects.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a process for recycling PSA desorption gas and catalytic regeneration flue gas in an oil refinery.
Background
Some important hydrogen-containing gases of petrochemical enterprises, such as PSA (pressure swing adsorption) desorption gas of a hydrogen production device and top gas of a depentanizer of reformate of a continuous reforming device, are not recovered and are burnt by a fuel gas system; meanwhile, the regenerated flue gas of the catalytic cracking unit and the PSA desorption gas of the hydrogen production unit have large flow and CO2High concentration, containing CO2At most, the method is the important target of emission reduction of petrochemical enterprises. And the catalytic regeneration flue gas has high nitrogen content almost close to that of air, and is also a resource. Table 1 shows typical compositions of the regenerated flue gas and PSA stripping gas from a hydrogen production plant after desulfurization and denitrification in an existing catalytic cracking plant.
TABLE 1 typical composition of flue gas and PSA Desorption gas after desulfurization and denitration
Therefore, how to recycle H in the waste gas2、N2CO, and CO reduction2Venting is a problem that one skilled in the art needs to address.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a process for recycling PSA desorption gas and catalytic regeneration flue gas in an oil refinery.
The purpose of the invention is realized by the following technical scheme:
a process for recycling PSA desorption gas and catalytic regeneration flue gas in an oil refinery comprises the following specific steps:
(1) PSA desorption gas is compressed by a PSA desorption gas compressor 1, then is heated by a feed gas-low pressure steam heat exchanger 2, is mixed with process steam, then is fed into a hydrocarbon steam hydrogen production conversion furnace 3, and reacts under the action of a catalyst to generate conversion gas;
(2) the catalytic regeneration flue gas is firstly purified and dedusted by the flue gas purification unit 5 to reach the dust content of less than or equal to 1mg/Nm3After the standard of the pressure is satisfied, the mixture enters a flash tank 6 to be flashed to obtain liquid, and then is compressed by a regeneration flue gas compressor 7 of a catalytic cracking unit and then enters a low-pressure steam heater 8 to be heated;
(3) the regeneration flue gas from the low-pressure steam heater and the reformed gas from the hydrocarbon steam hydrogen-making reformer are mixed and enter a medium-temperature shift reactor 9, and react under the action of a catalyst to obtain shift gas;
(4) the shift gas in the step (3) is subjected to heat exchange and temperature reduction through a low-pressure steam generator 10, a shift gas-deoxygenated water heat exchanger 11 and a circulating water cooler 13 in sequence, then a shift gas-water separation tank 14 is obtained, the separated shift gas enters a low-temperature methanol washing unit 15, and water is used for supplementing produced steam;
(5) the transformed gas enters a low-temperature methanol washing unit to recover CO2The obtained purified gas of the product enters a methanation unit 16, and the acid gas rich in sulfur enters a sulfur production unit;
(6) the purified gas of the product obtained in the step (5) is sent to an ammonia synthesis unit 17 after being sent to a methanation unit to remove total carbon, and NH is obtained through cyclic reaction under the catalysis3And (5) producing the product.
Further, the pressure after the compression by the PSA desorption gas compressor in the step (1) is 3.5MPa, the heating refers to heating to 164 ℃, and the water-carbon ratio of the hydrocarbon steam hydrogen production conversion furnace after the mixing with the process steam is 2.67.
Further, in the step (2), the pressure after the compression by the regeneration flue gas compressor of the catalytic cracking unit is 3.0MPa, and the heating refers to heating to 164 ℃.
Compared with the prior art, the process has the following advantages and beneficial effects:
(1) realizes the efficient utilization of hydrogen, hydrocarbon materials and CO in the hydrogen production desorption gas, and adjusts the prior process as fuel gas to produce H2；
(2) CO in concentrated catalytic regeneration flue gas and hydrogen production desorption gas2The purity is more than 99 percent, so that petrochemical enterprises can capture CO2The realization of essential emission reduction becomes possible;
(3) skillfully utilizes N in catalytic flue gas2The high energy consumption air separation unit which is necessary to be matched with the traditional ammonia synthesis process is saved;
(4) the hydrocarbon steam conversion hydrogen production, the flue gas purification and the ammonia synthesis are mature industrial processes and are easy to implement.
Drawings
FIG. 1 is a process flow diagram of a process for recycling PSA desorption gas and catalytic regeneration flue gas in an oil refinery according to an embodiment of the present invention;
the numbering in the figures is as follows:
1-PSA desorption gas compressor; 2-raw gas-low pressure steam heat exchanger; 3-a reformer for producing hydrogen from hydrocarbon steam; 4-medium pressure steam generator; 5-a flue gas purification unit; 6-a flash tank; 7-catalytic cracking unit regeneration flue gas compressor; 8-low pressure steam heater; 9-medium temperature shift reactor; 10-low pressure steam generator; 11-a heat exchanger for changing gas and removing oxygen water; 12-a diverter valve; 13-a circulating water cooler; 14-shift gas-water separation tank; 15-low temperature methanol wash unit; 16-a methanation unit; 17-ammonia synthesis unit.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Examples
The process flow chart of the recycling process of the PSA desorption gas and the catalytic regeneration flue gas in the refinery according to the present embodiment is shown in fig. 1. The method comprises the following specific steps:
(1) PSA desorption gas (69.2t/h,0.04MPa,30 ℃) is compressed to 3.5MPa by a PSA desorption gas compressor 1, enters a raw material gas-low pressure steam heat exchanger 2, is heated to 164 ℃, is mixed with process steam (15.1t/h,3.5MPa,300 ℃) (the water-carbon ratio is controlled to be 2.67) enters a hydrocarbon steam hydrogen production conversion furnace 3, and reacts under the action of a catalyst Z-417/Z-418 to generate conversion gas (84.5t/h,3.05MPa,850 ℃), and the composition of the obtained conversion gas is shown in Table 2; the reformed gas enters a medium-pressure steam (3.5MPa steam) generator 4 to generate steam, and then enters a medium-temperature shift reactor 9 when the temperature is 364.8 ℃;
TABLE 2 composition of the above reformed gas
(2) The catalytic regeneration flue gas (27.3t/h,0.04MPa,30 ℃) is firstly purified and dedusted by the flue gas purification unit 5 to reach the dust content less than or equal to 1mg/Nm3After the standard of/h, the mixed gas enters a flash tank 6 to be flashed out to obtain liquid, then the liquid is compressed to 3.0MPa by a regeneration flue gas compressor 7 of a catalytic cracking unit, and then the liquid is heated by a low-pressure steam (1.0MPa steam) heater 8, and the temperature is raised to 164 ℃;
(3) the regeneration flue gas (27.3t/h,3MPa,164 ℃) from the low-pressure steam heater and the converted gas (84.5t/h,3.05MPa,850 ℃) from the hydrocarbon steam hydrogen production converter are mixed and enter the medium-temperature shift reactor 9, and react under the action of a catalyst FB123 to obtain shifted gas (109.9t/h,3MPa,395.5 ℃), and the composition of the obtained shifted gas is shown in Table 3;
TABLE 3 composition of the above-mentioned transformed gas
| No. | Components | /％v |
| 1 | H2 | 43.6 |
| 2 | N2 | 14.5 |
| 3 | CO | 364ppm |
| 4 | CO2 | 39 |
| 5 | CH4 | 2.8 |
| 6 | C2H6 | / |
| 7 | C3H8 | / |
| 8 | iC4H10 | / |
| 9 | nC4H10 | / |
| 10 | nC5H12 | / |
| 11 | nC6H14 | / |
| 12 | H2O | 0.1 |
| 13 | H2S | / |
| Total up to | 100 |
(4) The converted gas in the step (3) is subjected to heat exchange and temperature reduction to 30 ℃ through a low-pressure steam (1.0MPa steam) generator 10, a converted gas-deoxygenated water heat exchanger 11 and a circulating water cooler 13 in sequence, then enters a converted gas-water separation tank 14, the separated converted gas enters a low-temperature methanol washing unit 15, and water is supplemented to generate steam; deoxygenated water (51.7t/h,30 ℃) enters a conversion gas-deoxygenated water heat exchanger 11, is divided by a flow dividing valve 12, and then enters a low-pressure steam (1.0MPa steam) generator 10 for one strand (17.4t/h) and enters a medium-pressure steam (3.5MPa steam) generator 4 for one strand (34.3 t/h);
(5) the converted gas enters a low-temperature methanol washing unit for recovery at 93.095t/h (turn over 78.2X 10)4t/yr) concentration of 99.28% CO2The obtained product purified gas (24.8t/h,2.7MPa,30 ℃) is subjected to methanationA unit 16 for the sour gas rich in sulphur to a sulphur unit;
(6) the purified gas of the product in the step (5) is sent to an ammonia synthesis unit 17 after entering a methanation unit to remove total carbon (24.8t/h,2.6MPa,80 ℃), and NH is obtained by circular reaction under the catalysis3The product is 21.2t/h (17.8 is multiplied by 10)4t/yr)。
Table 4 shows the theoretical hydrogen nitrogen requirement for the different ammonia production steps in step (6).
TABLE 4 theoretical requirement for Hydrogen and Nitrogen for different yield Ammonia Synthesis step
Table 5 shows the hydrogen, nitrogen and CO in the regeneration flue gas and the stripping gas calculated based on the processing amount of the process of the present example and the compositions in Table 12And (4) distribution.
TABLE 5 Hydrogen, Nitrogen and CO in the gas2Distribution of
Calculated based on catalytic cracking coke rate 8%.
From the above results, it can be seen that a set of 15X 10 is obtained from the viewpoint of material balance4Nm3Hydrogen production device and 12.5 multiplied by 10 set4Direct and latent N contained in stripping gas and regeneration flue gas of t/yr catalytic cracking unit2And H2The resource can be 17.8 multiplied by 10 per set of annual output4t synthesis ammonia plant provides nitrogen and hydrogen while recovering 78.2 x 104CO with a t/yr concentration of 99.28%2(corresponding to CO contained in desorption gas and regeneration flue gas2All recovered).
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (3)
1. A process for recycling PSA desorption gas and catalytic regeneration flue gas in an oil refinery is characterized by comprising the following specific steps:
(1) PSA desorption gas is compressed by a PSA desorption gas compressor, then is heated by a feed gas-low pressure steam heat exchanger, is mixed with process steam, then is fed into a hydrocarbon steam hydrogen production conversion furnace, and reacts under the action of a catalyst to generate conversion gas;
(2) purifying and dedusting the catalytic regeneration flue gas by a flue gas purification unit, entering a flash tank after the dust content is less than or equal to 1 mg/Nm/h standard, and then compressing the catalytic regeneration flue gas by a catalytic cracking unit regeneration flue gas compressor and heating the catalytic regeneration flue gas by a low-pressure steam heater;
(3) mixing the regenerated flue gas from the low-pressure steam heater and the reformed gas from the hydrocarbon steam hydrogen-making reformer, introducing the mixture into a medium-temperature shift reactor, and reacting under the action of a catalyst to obtain shift gas;
(4) the converted gas in the step (3) enters a converted gas-water separation tank after being subjected to heat exchange and temperature reduction through a low-pressure steam generator, a converted gas-deoxygenated water heat exchanger and a circulating water cooler in sequence, the separated converted gas enters a low-temperature methanol washing unit, and water replenishes produced steam;
(5) the transformed gas enters a low-temperature methanol washing unit to recover CO2The obtained product purified gas enters a methanation unit, and the acid gas rich in sulfur enters a sulfur production unit;
(6) feeding the purified gas of the step (5) into a methanation unit to remove total carbon, then feeding the purified gas into an ammonia synthesis unit, and carrying out cyclic reaction under the catalytic action to obtain NH3And (5) producing the product.
2. The process of claim 1 for recycling PSA desorption gas and catalytic regeneration flue gas from an oil refinery, which is characterized in that: in the step (1), the pressure after compression by the PSA desorption gas compressor is 3.5MPa, the heating refers to heating to 164 ℃, and the water-carbon ratio of the hydrocarbon steam hydrogen production conversion furnace after mixing with the process steam is 2.67.
3. The process of claim 1 for recycling PSA desorption gas and catalytic regeneration flue gas from an oil refinery, which is characterized in that: in the step (2), the pressure after compression by the regeneration flue gas compressor of the catalytic cracking unit is 3.0MPa, and the heating refers to heating to 164 ℃.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011198A (en) * | 2012-12-20 | 2013-04-03 | 赛鼎工程有限公司 | Process for preparing synthetic ammonia with coke-oven gas |
| CN104411622A (en) * | 2012-06-25 | 2015-03-11 | 乔治洛德方法研究和开发液化空气有限公司 | Method and installation for the combined production of ammonia synthesis gas and carbon dioxide |
| CN105189340A (en) * | 2013-05-10 | 2015-12-23 | 卡萨尔公司 | A process for producing ammonia synthesis gas with high temperature shift and low steam-to-carbon ratio |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411622A (en) * | 2012-06-25 | 2015-03-11 | 乔治洛德方法研究和开发液化空气有限公司 | Method and installation for the combined production of ammonia synthesis gas and carbon dioxide |
| CN103011198A (en) * | 2012-12-20 | 2013-04-03 | 赛鼎工程有限公司 | Process for preparing synthetic ammonia with coke-oven gas |
| CN105189340A (en) * | 2013-05-10 | 2015-12-23 | 卡萨尔公司 | A process for producing ammonia synthesis gas with high temperature shift and low steam-to-carbon ratio |
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